Lovely Professional University

TERM PAPER

CHEMISTRY:CHE 101

Submitted to: - Dr.O.P.Nautiyal Submitted by:-

Mr. Abhishek Kumar Mishra

Section : D4004

Roll no: RD4004A17

REG. no:11007175
 TOPIC: CARBON NANOTUBES
INTRODUCTION:

Carbon nanotubes (CNTs; also known as buckytubes) are allotropes of carbon with
a cylindrical nanostructure. Nanotubes have been constructed with length-to-diameter
ratio of up to 132,000,000:1, which is significantly larger than any other material.
These cylindrical carbon molecules have novel properties which make them
potentially useful in many applications in nanotechnology, electronics, optics, and
other fields of materials science, as well as potential uses in architectural fields. They
may also have applications in the construction of body armor. They exhibit
extraordinary strength and unique electrical properties, and are efficient thermal
conductors.

Nanotubes are members of the fullerene structural family, which also includes the
spherical buckyballs. The ends of a nanotube may be capped with a hemisphere of the
buckyball structure. Their name is derived from their size, since the diameter of a
nanotube is on the order of a few nanometers (approximately 1/50,000th of the width
of a human hair), while they can be up to 18 centimeters in length (as of 2010).
Nanotubes are categorized as single-walled nanotubes (SWNTs) and multi-walled
nanotubes (MWNTs).

Applied quantum chemistry, specifically, orbital hybridization best

describes chemical bonding in nanotubes. The chemical bonding of nanotubes is
composed entirely of sp2 bonds, similar to those of graphite. These bonds, which are
stronger than the sp3 bonds found in diamonds, provide nanotubules with their unique
strength. Moreover, nanotubes naturally align themselves into "ropes" held together
by van der Waals forces.

CONTENTS:
Types and Nanotubes and their related structure:
Single-walled Nanotube:

Most single-walled nanotubes (SWNT) have a diameter of close to 1 nanometer, with

a tube length that can be many millions of times longer. The structure of a SWNT can
be conceptualized by wrapping a one-atom-thick layer of graphite called graphene
into a seamless cylinder. The way the graphene sheet is wrapped is represented by a
pair of indices (n,m) called the chiral vector. The integers n and m denote the number
of unit vectors along two directions in the honeycomb crystal lattice of graphene. If m
= 0, the nanotubes are called "zigzag". If n = m, the nanotubes are called "armchair".
Otherwise, they are called "chiral". The diameter of a nanotube can be calculated
from its (n,m) indices as follows

where a = 0.246 nm.

Single-walled nanotubes are an important variety of carbon nanotube because they

exhibit electric properties that are not shared by the multi-walled carbon nanotube
(MWNT) variants. In particular, their band gap can vary from zero to about 2 eV and
their electrical conductivity can show metallic or semiconducting behavior, whereas
MWNTs are zero-gap metals. Single-walled nanotubes are the most likely candidate
for miniaturizing electronics beyond the micro electromechanical scale currently used
in electronics. The most basic building block of these systems is the electric wire, and
SWNTs can be excellent conductors One useful application of SWNTs is in the
development of the first intramolecular field effect transistors (FET). Production of
the first intramolecular logic gate using SWNT FETs has recently become possible as
well.] To create a logic gate you must have both a p-FET and an n-FET. Because
SWNTs are p-FETs when exposed to oxygen and n-FETs otherwise, it is possible to
protect half of an SWNT from oxygen exposure, while exposing the other half to
oxygen. This results in a single SWNT that acts as a NOT logic gate with both p and
n-type FETs within the same molecule.

Single-walled nanotubes are dropping precipitously in price, from around $1500 per
gram as of 2000 to retail prices of around $50 per gram of as-produced 40–60% by
weight SWNTs as of March 2010
Multi-walled Nanotube:

Multi-walled nanotubes (MWNT) consist of multiple rolled layers (concentric tubes)

of graphite. There are two models which can be used to describe the structures of
multi-walled nanotubes. In the Russian Doll model, sheets of graphite are arranged in
concentric cylinders, e.g. a (0,8) single-walled nanotube (SWNT) within a larger
(0,17) single-walled nanotube. In the Parchmett model, a single sheet of graphite is
rolled in around itself, resembling a scroll of parchment or a rolled newspaper. The
interlayer distance in multi-walled nanotubes is close to the distance between
graphene layers in graphite, approximately 3.4 Å.

The special place of double-walled carbon nanotubes (DWNT) must be emphasized

here because their morphology and properties are similar to SWNT but their
resistance to chemicals is significantly improved. This is especially important when
functionalization is required (this means grafting of chemical functions at the surface
of the nanotubes) to add new properties to the CNT. In the case of SWNT, covalent
functionalization will break some C=C double bonds, leaving "holes" in the structure
on the nanotube and thus modifying both its mechanical and electrical properties. In
the case of DWNT, only the outer wall is modified. DWNT synthesis on the gram-
scale was first proposed in 2003 by the CCVD technique, from the selective reduction
of oxide solutions in methane and hydrogen.

Torus

A nanotorus is theoretically described as carbon nanotube bent into a torus (doughnut

shape). Nanotori are predicted to have many unique properties, such as magnetic
moments 1000 times larger than previously expected for certain specific radii.
Properties such as magnetic moment, thermal stability, etc. vary widely depending on
radius of the torus and radius of the tube

Nanobud

Carbon nanobuds are a newly created material combining two previously discovered
allotropes of carbon: carbon nanotubes and fullerenes. In this new material, fullerene-
like "buds" are covalently bonded to the outer sidewalls of the underlying carbon
nanotube. This hybrid material has useful properties of both fullerenes and carbon
nanotubes. In particular, they have been found to be exceptionally good field emitters.
In composite materials, the attached fullerene molecules may function as molecular
anchors preventing slipping of the nanotubes, thus improving the composite’s
mechanical properties.

A stable nanobud structure

Cup stacked carbon nanotubes

Cup-stacked carbon nanotubes (CSCNTs) differ from other quasi-1D carbon

structures that normally behave as a metallic conductor of electrons. CSCNTs exhibit
semiconducting behaviors due to the stacking microstructure of graphene layers

Extreme carbon nanotubes

Cycloparaphenylene

The observation of the longest carbon nanotubes (18.5 cm long) was reported in 2009.
They were grown on Si substrates using an improved chemical vapor deposition
(CVD) method and represent electrically uniform arrays of single-walled carbon
nanotubes.

The shortest carbon nanotube is the organic compound cycloparaphenylene which

was synthesized in early 2009.

The thinnest carbon nanotube is armchair (2,2) CNT with a diameter of 3 Å. This
nanotube was grown inside a multi-walled carbon nanotube. Assigning of carbon
nanotube type was done by combination of high-resolution transmission electron
microscopy (HRTEM), Raman spectroscopy and density functional theory (DFT)
calculations.

The thinnest freestanding single-walled carbon nanotube is about 4.3 Å in diameter.

Researchers suggested that it can be either (5,1) or (4,2) SWCNT, but exact type of
carbon nanotube remains questionable. (3,3), (4,3) and (5,1) carbon nanotubes (all
about 4 Å in diameter) were unambiguously identified using more precise aberration-
corrected high-resolution transmission electron microscopy. However, they were
found inside of double-walled carbon nanotubes

Properties:

Strength:

Carbon nanotubes are the strongest and stiffest materials yet discovered in terms of
tensile strength and elastic modulus respectively. This strength results from the
covalent sp² bonds formed between the individual carbon atoms. In 2000, a multi-
walled carbon nanotube was tested to have a tensile strength of 63 gigapascals (GPa).
(This, for illustration, translates into the ability to endure tension of a weight
equivalent to 6422 kg on a cable with cross-section of 1 mm2.) Since carbon
nanotubes have a low density for a solid of 1.3 to 1.4 g·cm−3, its specific strength of
up to 48,000 kN·m·kg−1 is the best of known materials, compared to high-carbon
steel's 154 kN·m·kg−1.

Under excessive tensile strain, the tubes will undergo plastic deformation, which
means the deformation is permanent. This deformation begins at strains of
approximately 5% and can increase the maximum strain the tubes undergo before
fracture by releasing strain energy.

CNTs are not nearly as strong under compression. Because of their hollow structure
and high aspect ratio, they tend to undergo buckling when placed under compressive,
torsional or bending stress.

Comparison of mechanical properties

Young's modulus Tensile strength Elongation at break
Material
(TPa) (GPa) (%)
SWNT ~1 (from 1 to 5) 13–53E 16
Armchair
0.94T 126.2T 23.1
SWNT
Zigzag SWNT 0.94T 94.5T 15.6–17.5
 Chiral SWNT 0.92
MWNT 0.27 –0.8E[–0.95E
E
11E–63E–150E
Stainless steel 0.186E–0.214E 0.38E–1.55E 15–50
Kevlar–29&149 0.06E–0.18E 3.6E–3.8E ~2

E
Experimental observation; TTheoretical prediction

The above discussion referred to axial properties of the nanotube, whereas simple
geometrical considerations suggest that carbon nanotubes should be much softer in
the radial direction than along the tube axis. Indeed, TEM observation of radial
elasticity suggested that even the van der Waals forces can deform two adjacent
nanotubes. Nanoindentation experiments, performed by several groups on multiwalled
carbon nanotubes, indicated Young's modulus of the order of several GPa confirming
that CNTs are indeed rather soft in the radial direction

Hardness:

Diamond is considered to be the hardest material. Under conditions of high

temperature and high pressure, graphite transforms into diamond. One study
succeeded in the synthesis of a super-hard material by compressing SWNTs to above
24 GPa at room temperature. The hardness of this material was measured with a
nanoindenter as 62–152 GPa. The hardness of reference diamond and boron nitride
samples was 150 and 62 GPa, respectively. The bulk modulus of compressed SWNTs
was 462–546 GPa, surpassing the value of 420 GPa for diamond

Kinetic:

Multi-walled nanotubes are multiple concentric nanotubes precisely nested within one
another. These exhibit a striking telescoping property whereby an inner nanotube core
may slide, almost without friction, within its outer nanotube shell, thus creating an
atomically perfect linear or rotational bearing. This is one of the first true examples of
molecular nanotechnology, the precise positioning of atoms to create useful machines.
Already, this property has been utilized to create the world's smallest rotational motor.
Future applications such as a gigahertz mechanical oscillator are also envisaged

Electrical:

Band structures computed using tight binding approximation for (6,0) CNT (zigzag,
metallic) (10,2) CNT (semiconducting) and (10,10) CNT (armchair, metallic).

Because of the symmetry and unique electronic structure of graphene, the structure of
a nanotube strongly affects its electrical properties. For a given (n,m) nanotube, if n =
m, the nanotube is metallic; if n − m is a multiple of 3, then the nanotube is
semiconducting with a very small band gap, otherwise the nanotube is a moderate
semiconductor. Thus all armchair (n = m) nanotubes are metallic, and nanotubes (6,4),
(9,1), etc. are semiconducting

Thermal
All nanotubes are expected to be very good thermal conductors along the tube,
exhibiting a property known as "ballistic conduction", but good insulators laterally to
the tube axis. Measurements show that a SWNT has a room-temperature thermal
conductivity along its axis of about 3500 W·m−1·K−1; compare this to copper, a metal
well-known for its good thermal conductivity, which transmits 385 W·m−1·K−1. A
SWNT has a room-temperature thermal conductivity across its axis of about 1.52
W·m−1·K−1, which is about as thermally conductive as soil. The temperature stability
of carbon nanotubes is estimated to be up to 2800 °C in vacuum and about 750 °C in
air

Defects

As with any material, the existence of a crystallographic defect affects the material
properties. Defects can occur in the form of atomic vacancies. High levels of such
defects can lower the tensile strength by up to 85%. Another form of carbon nanotube
defect is the Stone Wales defect, which creates a pentagon and heptagon pair by
rearrangement of the bonds. Because of the very small structure of CNTs, the tensile
strength of the tube is dependent on its weakest segment in a similar manner to a
chain, where the strength of the weakest link becomes the maximum strength of the
chain.

Crystallographic defects also affect the tube's electrical properties. A common result
is lowered conductivity through the defective region of the tube. A defect in armchair-
type tubes (which can conduct electricity) can cause the surrounding region to become
semiconducting, and single monoatomic vacancies induce magnetic properties.

Crystallographic defects strongly affect the tube's thermal properties. Such defects
lead to phonon scattering, which in turn increases the relaxation rate of the phonons.
This reduces the mean free path and reduces the thermal conductivity of nanotube
structures. Phonon transport simulations indicate that substitutional defects such as
nitrogen or boron will primarily lead to scattering of high-frequency optical phonons.
However, larger-scale defects such as Stone Wales defects cause phonon scattering
over a wide range of frequencies, leading to a greater reduction in thermal
conductivity

One-dimensional transport

Because of the nanoscale dimensions, electrons propagate only along the tube's axis
and electron transport involves many quantum effects. Because of this, carbon
nanotubes are frequently referred to as “one-dimensional”.

Toxicity

Determining the toxicity of carbon nanotubes has been one of the most pressing
questions in nanotechnology. Unfortunately, such research has only just begun. Thus,
the data are still fragmentary and subject to criticism. Preliminary results highlight the
difficulties in evaluating the toxicity of this heterogeneous material. Parameters such
as structure, size distribution, surface area, surface chemistry, surface charge, and
agglomeration state as well as purity of the samples, have considerable impact on the
reactivity of carbon nanotubes. However, available data clearly show that, under some
conditions, nanotubes can cross membrane barriers, which suggests that if raw
materials reach the organs they can induce harmful effects such as inflammatory and
fibrotic reactions.

A study led by Alexandra Porter from the University of Cambridge shows that CNTs
can enter human cells and accumulate in the cytoplasm, causing cell death.

Results of rodent studies collectively show that regardless of the process by which
CNTs were synthesized and the types and amounts of metals they contained, CNTs
were capable of producing inflammation, epithelioid granulomas (microscopic
nodules), fibrosis, and biochemical/toxicological changes in the lungs. Comparative
toxicity studies in which mice were given equal weights of test materials showed that
SWCNTs were more toxic than quartz, which is considered a serious occupational
health hazard when chronically inhaled. As a control, ultrafine carbon black was
shown to produce minimal lung responses.

The needle-like fiber shape of CNTs, similar to asbestos fibers, raises fears that
widespread use of carbon nanotubes may lead to mesothelioma, cancer of the lining of
the lungs often caused by exposure to asbestos. A recently-published pilot study
supports this prediction. Scientists exposed the mesothelial lining of the body cavity
of mice, as a surrogate for the mesothelial lining of the chest cavity, to long
multiwalled carbon nanotubes and observed asbestos-like, length-dependent,
pathogenic behavior which included inflammation and formation of lesions known as
granulomas. Authors of the study conclude:

"This is of considerable importance, because research and business

communities continue to invest heavily in carbon nanotubes for a wide range
of products under the assumption that they are no more hazardous than
graphite. Our results suggest the need for further research and great caution
before introducing such products into the market if long-term harm is to be
avoided."

According to co-author Dr. Andrew Maynard:

"This study is exactly the kind of strategic, highly focused research needed to
ensure the safe and responsible development of nanotechnology. It looks at a
specific nanoscale material expected to have widespread commercial
applications and asks specific questions about a specific health hazard. Even
though scientists have been raising concerns about the safety of long, thin
carbon nanotubes for over a decade, none of the research needs in the current
U.S. federal nanotechnology environment, health and safety risk research
strategy address this question."

Although further research is required, results presented today clearly demonstrate that,
under certain conditions, especially those involving chronic exposure, carbon
nanotubes can pose a serious risk to human health

Potential applications
Main article: Potential applications of carbon nanotubes
See also, for last current applications: Timeline of carbon nanotubes
The joining of two carbon nanotubes with different electrical properties to form a
diode has been proposed . L Chico et al. Phys Rev Lett 76, 971 (1996)

The strength and flexibility of carbon nanotubes makes them of potential use in
controlling other nanoscale structures, which suggests they will have an important
role in nanotechnology engineering. The highest tensile strength of an individual
multi-walled carbon nanotube has been tested to be is 63 GPa. Carbon nanotubes were
found in Damascus steel from the 17th century, possibly helping to account for the
legendary strength of the swords made of it.

Structural:

Because of the carbon nanotube's superior mechanical properties, many structures

have been proposed ranging from everyday items like clothes and sports gear to
combat jackets and space elevators. However, the space elevator will require further
efforts in refining carbon nanotube technology, as the practical tensile strength of
carbon nanotubes can still be greatly improved.

In electrical circuits

Nanotube based transistors, also known as CNTFETs, have been made that operate at
room temperature and that are capable of digital switching using a single electron.
However, one major obstacle to realization of nanotubes has been the lack of
technology for mass production. In 2001 IBM researchers demonstrated how metallic
nanotubes can be destroyed, leaving semiconducting ones behind for use as
transistors. Their process is called "constructive destruction" which includes the
automatic destruction of defective nanotubes on the wafer. This process, however,
only gives control over the electrical properties on a statistical scale.

The first nanotube integrated memory circuit was made in 2004. One of the main
challenges has been regulating the conductivity of nanotubes. Depending on subtle
surface features a nanotube may act as a plain conductor or as a semiconductor. A
fully automated method has however been developed to remove non-semiconductor
tubes

As paper batteries

A paper battery is a battery engineered to use a paper-thin sheet of cellulose (which is

the major constituent of regular paper, among other things) infused with aligned
carbon nanotubes. The nanotubes act as electrodes; allowing the storage devices to
conduct electricity. The battery, which functions as both a lithium-ion battery and a
supercapacitor, can provide a long, steady power output comparable to a conventional
battery, as well as a supercapacitor’s quick burst of high energy—and while a
conventional battery contains a number of separate components, the paper battery
integrates all of the battery components in a single structure, making it more energy
efficient

Current applications

The current use and application of nanotubes has mostly been limited to the use of
bulk nanotubes, which is a mass of rather unorganized fragments of nanotubes. Bulk
nanotube materials may never achieve a tensile strength similar to that of individual
tubes, but such composites may nevertheless yield strengths sufficient for many
applications. Bulk carbon nanotubes have already been used as composite fibers in
polymers to improve the mechanical, thermal and electrical properties of the bulk
product.

Easton-Bell Sports, Inc. have been in partnership with Zyvex Performance Materials,
using CNT technology in a number of their bicycle components—including flat and
riser handlebars, cranks, forks, seatposts, stems and aero bars.

Zyvex Performance Materials has also built a 54' maritime vessel, the Piranha
Unmanned Surface Vessel, as a technology demonstrator for what is possible using
CNT technology. CNTs help improve the structural performance of the vessel,
resulting in a lightweight 8,000lb boat.

Solar cells

Solar cells developed at the New Jersey Institute of Technology use a carbon
nanotube complex, formed by a mixture of carbon nanotubes and carbon buckyballs
(known as fullerenes) to form snake-like structures. Buckyballs trap electrons,
although they can't make electrons flow. Add sunlight to excite the polymers, and the
buckyballs will grab the electrons. Nanotubes, behaving like copper wires, will then
be able to make the electrons or current flow.

Ultracapacitors

MIT Laboratory for Electromagnetic and Electronic Systems uses nanotubes to

improve ultracapacitors. The activated charcoal used in conventional ultracapacitors
has many small hollow spaces of various size, which create together a large surface to
store electric charge. But as charge is quantized into elementary charges, i.e.
electrons, and each such elementary charge needs a minimum space, a significant
fraction of the electrode surface is not available for storage because the hollow spaces
are not compatible with the charge's requirements. With a nanotube electrode the
spaces may be tailored to size—few too large or too small—and consequently the
capacity should be increased considerably.
Other applications

Aligned nanotubes are preferred for many applications.

Carbon nanotubes have been implemented in nanoelectromechanical systems,

including mechanical memory elements (NRAM being developed by Nantero Inc.)
and nanoscale electric motors (see Nanomotor).

In May 2005, Nanomix Inc placed on the market a hydrogen sensor which integrated
carbon nanotubes on a silicon platform. Since then Nanomix has been patenting many
such sensor applications such as in the field of carbon dioxide, nitrous oxide, glucose,
DNA detection, etc.

Eikos Inc of Franklin, Massachusetts and Unidym Inc. of Silicon Valley, California
are developing transparent, electrically conductive films of carbon nanotubes to
replace indium tin oxide (ITO). Carbon nanotube films are substantially more
mechanically robust than ITO films, making them ideal for high-reliability
touchscreens and flexible displays. Printable water-based inks of carbon nanotubes
are desired to enable the production of these films to replace ITO. Nanotube films
show promise for use in displays for computers, cell phones, PDAs, and ATMs.

A nanoradio, a radio receiver consisting of a single nanotube, was demonstrated in

2007. In 2008 it was shown that a sheet of nanotubes can operate as a loudspeaker if
an alternating current is applied. The sound is not produced through vibration but
thermoacoustically.

Because of the high mechanical strength of carbon nanotubes, research is being made
into weaving them into clothes to create stab-proof and bulletproof clothing. The
nanotubes would effectively stop the bullet from penetrating the body, although the
bullet's kinetic energy would likely cause broken bones and internal bleeding.

A flywheel made of carbon nanotubes could be spun at extremely high velocity on a

floating magnetic axis in a vacuum, and potentially store energy at a density
approaching that of conventional fossil fuels. Since energy can be added to and
removed from flywheels very efficiently in the form of electricity, this might offer a
way of storing electricity, making the electrical grid more efficient and variable power
suppliers (like wind turbines) more useful in meeting energy needs. The practicality
of this depends heavily upon the cost of making massive, unbroken nanotube
structures, and their failure rate under stress.
Ultra-short SWNTs (US-tubes) have been used as nanoscaled capsules for delivering
MRI contrast agents in vivo.

Nitrogen-doped carbon nanotubes may replace platinum catalysts used to reduce

oxygen in fuel cells. A forest of vertically-aligned nanotubes can reduce oxygen in
alkaline solution more effectively than platinum, which has been used in such
applications since the 1960s. The nanotubes have the added benefit of not being
subject to carbon monoxide poisoning.

Discovery
Carbon nanotubes were discovered by Iijima in 1991 A.D. using electron microscope
while studying cathodic material deposition trhough vapourizing carbon graphite in
an electical arc evaporation reactor under a inert atmosphere during the synthesis of
Fullerenes.The nanotubes produced by Iijima appeared to be made up of a perfect
network of hexagonal graphite.

A 2006 editorial written by Marc Monthioux and Vladimir Kuznetsov in the journal
Carbon described the interesting and often misstated origin of the carbon nanotube. A
large percentage of academic and popular literature attributes the discovery of hollow,
nanometer-size tubes composed of graphitic carbon to Sumio Iijima of NEC in 1991.

In 1952 L. V. Radushkevich and V. M. Lukyanovich published clear images of 50

nanometer diameter tubes made of carbon in the Soviet Journal of Physical
Chemistry. This discovery was largely unnoticed, as the article was published in the
Russian language, and Western scientists' access to Soviet press was limited during
the Cold War. It is likely that carbon nanotubes were produced before this date, but
the invention of the transmission electron microscope (TEM) allowed direct
visualization of these structures.

Carbon nanotubes have been produced and observed under a variety of conditions
prior to 1991. A paper by Oberlin, Endo, and Koyama published in 1976 clearly
showed hollow carbon fibers with nanometer-scale diameters using a vapor-growth
technique. Additionally, the authors show a TEM image of a nanotube consisting of a
single wall of graphene. Later, Endo has referred to this image as a single-walled
nanotube.

In 1979 John Abrahamson presented evidence of carbon nanotubes at the 14th

Biennial Conference of Carbon at Pennsylvania State University. The conference
paper described carbon nanotubes as carbon fibers which were produced on carbon
anodes during arc discharge. A characterization of these fibers was given as well as
hypotheses for their growth in a nitrogen atmosphere at low pressures.

REFERENCES:
1) Principles of nanotechnology by G. Ali Maansoori
2)www.nanotechnology .com
3)www.carbon nanotubes.com
4)www.nano.gov
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